WO2012076763A1

WO2012076763A1 - Blend of polymers having yield stress and use thereof for the manufacture of metal-polymer composites

Info

Publication number: WO2012076763A1
Application number: PCT/FR2010/052675
Authority: WO
Inventors: Marjolaine Doux; Laurence Lucchini; Didier VERCHÈRE; Florence Avril; Philippe Cassagnau; Daniel Sage
Original assignee: Arcelormittal Investigacion Y Desarrollo, S.L.
Priority date: 2010-12-10
Filing date: 2010-12-10
Publication date: 2012-06-14
Also published as: PL2649107T3; HUE032769T2; RU2571762C2; EP2649107B1; ES2623868T3; RU2013131781A; EP2649107A1

Abstract

The invention relates to a two-phase polymer blend, comprising: (a) a polyamide having a melting point at most equal to 210°C, (b) a polyolefin modified by grafting of carboxyl functions, the rheological behaviour of which in the melt state is characterized by the existence of a yield stress, and also to a process for the preparation thereof. The invention furthermore relates to the use of this polymer blend for the manufacture of composite structures and facings and also the resulting composite structures and facings.

Description

Threshold stress polymer blend and

The present invention relates to novel mixtures of threshold stress polymers and their use for the manufacture of metal-polymer composites.

[State of the art]

One of the avenues explored to reduce car consumption is the weight reduction of vehicles. In this context, an active research is conducted on the replacement of metal sheets with metal / polymer composites, such as metal / polymer / metal structures, also called sandwich structures, or polymer-coated metal facings.

The polymers used for these composites must meet many requirements, and in particular exhibit adhesion to the metal, have high rigidity and elongation greater than that of the metal.

In order to allow substantial lightening, the polymer must have a fairly large thickness, typically from 300 μm to several mm. It is therefore preferable to use an extrudable thermoplastic polymer rather than a thermosetting polymer which must be applied in solution.

Furthermore, the polymer used should be compatible with the cataphoresis step used in the automotive sector for painting. This process involves cooking up to 210 ° C for about 45 minutes. When the polymer becomes too fluid, it flows and causes the sliding of the metal sheets, which leads to the destruction of the composite.

The patent application WO 2005/014278 proposes sandwich structures comprising as a polymer a mixture of polyamide 6, modified polyethylene and styrene-maleic anhydride copolymer (SMA). This mixture has satisfactory properties, but its high melting point (220 ° C), and therefore its high temperature of implementation (240 ° C), makes it incompatible with some assembly equipment by bonding. Indeed, these devices are not able to achieve temperatures above 220 ° C necessary to melt the polymer mixture on the surface to allow the spreading of the polymer mixture on the metal and perfect adhesion to the metal. Furthermore, it has proved difficult to ensure the homogeneous distribution of the styrene-maleic anhydride copolymer (SMA) in the mixture, which affects the homogeneity of the morphology and the adhesion of the film. [Technical problem]

There is therefore a need for a polymeric mixture having the characteristics required for the manufacture of metal-polymer composites which does not have the disadvantages mentioned above. In particular, there is a need for a polymer mixture of simple formulation capable of withstanding the cataphoresis step at 210 ° C while having a melting point not exceeding 210 ° C.

[Summary of the Invention]

The invention follows from the idea of using a polymer mixture having a threshold stress fluid behavior, that is to say having even in the molten state a creep resistance sufficient to withstand the cataphoresis step .

An in-depth study has identified mixtures of polyamide and modified polyethylene with the properties required for application in terms of adhesion, stiffness and elongation, and which are in the melt state of the threshold stress fluids.

Also, according to a first aspect, the invention is directed to a biphasic polymer mixture, comprising:

(a) a polyamide having a melting point of at most 210 ° C,

(b) a modified polyolefin having carboxylic functions,

whose rheological behavior in the molten state is characterized by the existence of a threshold stress.

Preferably, the polymer mixture according to the invention comprises 30 to 70% by weight of polyamide. The polymer mixture furthermore advantageously comprises 30 to 70% by weight of modified polyolefin.

The modified polyolefin is preferably a modified polyethylene. Advantageously, it is a polyolefin modified with maleic anhydride. A polyolefin modified with 0.01 to 20% by weight of compound having carboxylic functions is particularly preferred.

Advantageously, the polyamide is a polyamide 11.

According to a preferred embodiment, the polymer mixture according to the invention comprises a continuous phase, also called matrix, composed essentially of polyamide and a co-continuous or dispersed phase composed essentially of polyolefin. When the phase is dispersed, it is preferably in the form of nodules, the average diameter of which is preferably less than 500 nm. When the mixture consists of only these two polymers, the polymer mixture is It is thus present in the form of a polyamide matrix in which the modified polyolefin is dispersed or forms a co-continuous phase.

Advantageously, the mixture according to the invention further comprises 5 to 20% by weight of fillers.

Preferably, the mixture according to the invention has a threshold stress of between 200 and 2000 Pa.

According to another aspect, the invention is directed to a process for preparing the polymer mixture described above comprising the steps of:

(a) providing a suitable amount of polyamide and an appropriate amount of modified polyolefin having carboxylic functions; and

(b) mixing the polyamide and the modified polyolefin at a temperature above the melting peak of the polyamide.

In yet another aspect, the invention provides a method of manufacturing a metal-polymer composite comprising the steps of:

(i) providing a first sheet of metal, optionally heated to the melting temperature of the polymeric mixture;

(ii) applying a polymer blend according to the invention to the first sheet of metal to form a metal-polymer composite;

(iii) optionally, applying a second metal sheet optionally heated to the polymer melt temperature, to the polymer blend to form a metal-polymer-metal composite; and

(iv) heating the composite until the polymer mixture melts in contact with the metal to complete the adhesion.

Also, according to another aspect, the invention is directed to sandwich structures comprising, between two metal sheets, a film of the polymeric mixture according to the invention as well as facings comprising a metal sheet coated with the polymer mixture according to the invention.

Finally, according to a last aspect, the invention provides a facing comprising a metal sheet coated with the polymer mixture according to the invention.

[Definitions]

Within the scope of this paper, the term "threshold stress fluid" is intended to mean a rheological behavior of a deformable material characterized by the fact that a flow takes place only above a certain value of stress, referred to as the threshold stress. . The concept of threshold stress is known for fluids in general and for polymers in the molten state in particular. Furthermore, the term "creep behavior" is understood to mean the absence of a deformation rate, for example by flow, of a material subjected to stress for a sufficient duration.

The term "polymeric mixture" is understood to mean a composition of several, in particular of two immiscible polymers. The polymers are for the most part immiscible with each other because of their high molar masses and / or adverse interactions. Polymer mixtures are therefore most often in the form of multiphase structures. In the case of mixing two polymers, two-phase mixtures may comprise a continuous phase and a dispersed phase. Most often, the majority polymer forms the continuous phase while the minority polymer forms the dispersed phase. When the polymers are present in similar proportions, one can also observe mixtures in which the two phases are both continuous called co-continuous. There are different types of morphologies in polymeric mixtures, including nodular morphology, fibrillar morphology, and lamellar morphology.

In principle, the mixture described in the present application is a physical mixture, not involving covalent bonds between the constituents. However, at the polymer interface, the terminal amino groups of the polyamide may form imide linkages with the carboxylic groups of the modified polyolefin, as will be discussed in more detail below.

The term "modified polyolefin" is intended to mean a polyolefin comprising polar and especially carboxylic groups. These groups may have been introduced into the polyolefin during the polymerization or afterwards. The resulting patterns can therefore be in the main chain or in the side chains of the modified polymer. In practice, the modified polyolefins are obtained by copolymerization of an olefin in the presence of suitable monomers or by reaction of the polyolefin with appropriate compounds, also called grafting. The unsaturated carboxylic acids and their derivatives, in particular their anhydride, constitute preferred monomers and / or compounds within the scope of the present invention.

The term "grafting rate" in the following refers to the mass concentration of compound used to modify the polyolefin in the modified polyolefin, relative to the final weight of the modified polyolefin. Unless otherwise indicated, this rate refers to the overall mass concentration in the polymer, without distinguishing whether it is present in the polymer or in monomeric form. [Components of the mixture]

The polymeric mixture described comprises at least two components, namely a polyamide and a modified polyolefin.

It may be advantageous in certain applications to add other constituents, for example, as will be explained later, mineral fillers that may further increase the threshold stress of the mixture.

However, in order to avoid any problem of incompatibility and / or homogeneity, the mixture is preferably composed of polyamide and grafted polyolefin and is devoid of any other polymer. Preferably, it is also devoid of any other compound capable of reacting with the constituents of the mixture or of reacting in a humid medium by degrading the adhesion or the stability of the mixture.

Without wishing to be bound by any theory, it is assumed that the threshold stress fluid behavior is related to the presence of a three-dimensional structure. With this structure, the fluid is able to withstand a stress less than τ ₀ . When the stress exceeds x _c , the three-dimensional structure is destroyed and the polymer flows.

In the polymeric mixture described, di-block copolymers are formed by reaction between the amine end groups of the polyamide and the carboxylic functions of the modified reactive groups on the polyolefin. The reaction at the interface of the polymers is schematically illustrated in FIG.

The copolymers thus formed in situ at the interfaces of the mixture can act as a compatibilizing agent, thus allowing better dispersion of the two phases and, where appropriate, smaller nodules closer to one another. The short internodular distance allows interaction between the copolymer chains of neighboring nodules by physical entanglement, forming a three-dimensional rubber network (see FIG. 2). This three-dimensional network formed by the internodular interaction limits the deformation under stress until its disappearance under a stress called threshold stress.

The polyamides are polymers containing amide functions (~ C (= O) -NH-) and can be obtained by:

(1) lactam polymerization with ring opening; or

(2) polycondensation of amino acids; or

(3) polycondensation of diamines with diacids.

The aliphatic polyamides are designated by one or more numbers relating to the number of carbon atoms contained in the repeating unit. So the PA 6 or PA11 is obtained by polycondensation of an amino acid or a lactam with respectively 6 or 11 carbon atoms in the unit. In PA 6-6 designations, the values correspond to the number of carbon atoms of the diamine and the diacid. The polyamides can be aliphatic, semi-aromatic (only one of the monomers is aromatic) or aromatic. Homopolymers formed from a single monomer are preferred, but polyamide copolymers obtained from several different monomers may also be contemplated.

Semi-crystalline polyamides are preferred over amorphous polyamides since they are more readily converted since they have a melting peak rather than a single softening point.

For the intended application, the melting point of the polyamide is advantageously between 160 and 210 ° C. According to a particular embodiment, the melting point of the polyamide is between 170 and 200 ° C.

Among the polyamides suitable for the mixture described, there may be mentioned in particular the polyamide 11 having a melting point of between 177 and 190 ° C, or the polyamide 2 having a melting point between 172 and 180 ° C.

The molar mass of the polyamide has an impact on the properties of the mixture since it determines the number of terminal amine groups available to form the copolymer in contact with the carboxylic functions of the modified polyolefin. The molar mass further influences the melting temperature. The molar mass of the polyamide is preferably in the range of from 1,000 to 100,000, preferably from 10,000 to 30,000 g / mol.

In practice, the melt index of the polyamide is preferably between 1 and 40, preferably 10 to 25 cm ^3/10 min under 2.16 kg at 235 ° C.

Commercially available polyamides often comprise 5 to 20% by weight, preferably 10 to 20% by weight of plasticizers. The addition of a plasticizer can help improve the impact resistance. As suitable plasticizers may be mentioned ε-caprolactam, N-butylbenzene sulfonamide, or cetyl paraoxybenzoate.

However, as mentioned above, the polymer mixture according to the invention preferably does not comprise additives other than those present where appropriate in the commercial polymers used and the mineral fillers discussed below.

The Newtonian viscosity of the polymers, and more specifically the viscosity ratio of the two basic constituents is also an important factor in order to obtain a mixture with satisfactory properties. Indeed, the viscosities influence the morphology of the mixture. An empirical rule recommends a ratio between the shear viscosity of the modified polyolefin and that of the polyamide between 1 and 10. The newtonian viscosity of the polyamide is preferably between 500 and 5000, preferably 1000 to 4000 Pa.s at 210 °. vs.

The mixture according to the invention generally comprises between 30 and 70% by weight, and more preferably between 40 and 65% by weight of polyamide. Below 30%, the proportion of polyamide is generally insufficient to impart to the polymer mixture the advantageous mechanical properties of the polyamide, whereas above 70%, there is a risk of no longer having enough modified polyolefin to favor the in-situ compatibility of the two constituents.

The modified polyolefin present in the mixture can be obtained from a thermoplastic polyolefin. The polyolefin may be chosen in particular from polyethylene, polypropylene, polymethylpentene and polybutene. Among these families will be chosen a polymer with appropriate properties in terms of rigidity, density and crystallinity.

The most preferred polyolefin is polyethylene. These may be homopolymers such as HDPE (High Density Polyethylene) or LDPE (Low Density Polyethylene) or LLDPE (Low Density Linear Polyethylene) or copolymers derived from polyethylene such as copolymers of ethylene and diene. octene.

In order to allow in situ compatibilization at the interfaces in the mixture, the polyolefin is modified with groups containing carboxylic functions. These groups may be introduced during the polymerization, by copolymerization in the presence of the appropriate monomers, or by grafting subsequent to the polymerization.

These groups containing carboxylic functions are in particular groups of carboxylic acids or derivatives such as, for example, unsaturated acids containing 1 to 6 carboxylic functions, such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, aconitrile acid and itaconic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, acrylic acid and methacrylic acid as well as anhydrides, salts and and corresponding esters. Preferably, the polyolefin is modified with maleic anhydride.

A large number of modified polyolefins having carboxylic functions are commercially available.

The melt index of the modified polyolefin is preferably between 0.1 and 30, preferably between 0.2 and 10 and especially between 0.2 and 2 cm ³ / 10min under 5Kg at 190 ° C in order to facilitate its mixture with polyamide. The modified polyolefins may be in the form of an ionomer, for example following the at least partial neutralization of the carboxylic functions.

The degree of grafting of the polyolefin is an important parameter since it can influence the threshold stress by affecting the number of bonds likely to form at the interface. Generally, it is sufficient that the degree of grafting of the polyolefin is between 0.01 and 20%, preferably between 0.02 and 0% and in particular between 0.05 and 5% by weight of carboxylic acid or of its derivative relative to the weight of the polyolefin.

The Newtonian viscosity of the modified polyolefin is preferably greater than 5000, and in particular at least 20,000 Pa.s at 220 ° C. However, the viscosity may be difficult to determine when the modified polyolefin exhibits an elastic solid type viscoelastic behavior.

The mixture according to the invention generally comprises between 30 and 70% by weight, and more preferably between 35 and 60% by weight of modified polyolefin. The threshold stress of the polymeric mixtures according to the invention can be further increased by adding mineral fillers.

The quantity of charges necessary to reveal a threshold stress is higher for spherical fillers without interaction between them than for structuring loads.

Structural loads are understood to mean elementary particles of nanometric size which form aggregates on a micrometric scale and which above a certain concentration form a network of charges (percolation phenomenon). These fillers may be spherical, such as nanostructured silicas, or high form factor, that is to say greater than 100, such as carbon nanotubes and exfoliated clays. The form factor is defined as the ratio of the largest dimension of the particle to its thickness.

By the addition of fillers, the desired threshold stress is maintained while increasing the amount of polyamide.

Some charges are particularly interesting because they also allow to confer one or more additional features to the mixture. Thus, the addition of carbon charges in different forms (carbon black, carbon fibers, graphite, carbon nanotubes) makes the polymer mixture conductive, which is interesting for some painting processes (see "Conductive polyphenylene ether / polyamide blends for electrostatic painting applications. JJ Scobbo, Antec'98, pp. 2468-2472). It may therefore be advantageous to add conductive fillers to the polymer mixture. In order to safeguard the properties of the polymer mixture, especially a low viscosity, it is preferable to maintain the proportion of charges at a reasonable value.

The proportion of fillers in the polymer mixture according to the invention can range from 0 to 30% by weight, and more particularly from 5 to 20% by weight of the total mixture.

[Preparation and properties of the mixture]

The polymeric mixture described is prepared in the simplest manner by thoroughly mixing the components at a temperature at which the polymer components are in the molten state. The intimate mixing can take place by various means known per se, for example in a Hake internal reactor or a twin-screw extruder.

The polymeric mixtures contemplated by the present invention have the melt behavior of threshold stress fluids, i.e., they flow only when the applied stress exceeds a certain threshold.

The study of the complex shear modulus (G * (a>) = G '((o) + jG "(co)) of these mixtures shows a plateau on the elastic modulus G' at low frequencies, that is, ie, less than 1 rad / sec As mentioned above, this phenomenon can be explained by the formation of a copolymer in situ at the interface of the polyamide and the modified polyolefin.

The value of the threshold stress measured according to the method described later is preferably at least 50 Pa, which approximately corresponds to the stress exerted by the weight of a 0.5 mm thick metal siding in a sandwich structure. . Advantageously, the threshold stress of the mixtures is between 200 and 2000 Pa.

Because the described polymeric mixture only flows when the stress exceeds the threshold stress, it can satisfy the irreconcilable a priori conditions posed by the thermal capacities of the rolling units and the resistance to cataphoresis.

The morphology of the polymeric mixture is, as mentioned above, preferably a continuous phase forming a matrix of a dispersed phase or a co-continuous phase. When the mixture comprises a dispersed phase, it is observed that the dispersed phase is most often in the form of nodules. However, the dispersed phase can also form fibers (fibrillar morphology) or layers (lamellar morphology).

Nodular morphology is however preferred. Indeed, such a morphology provides an extended polymer interface and thus the formation of a network important links to the interface, to ensure a high threshold constraint. Preferably, the average nodular diameter as determined experimentally by scanning electron microscopy (SEM) and image analysis is less than 500 nm, preferably less than 300 nm, in order to promote the interaction between the polymer chains to form a rubber network generating the threshold stress.

The compatibilization between the polyamide and the polyolefin is ensured by the in situ formation of copolymers formed by reaction between the terminal amine groups of the polyamides and the carboxylic functions of the modified polyolefin.

Preferably, the matrix continuous phase is composed essentially of polyamide while the dispersed or co-continuous phase is composed of the modified polyolefin. Such a morphology of the polymeric mixture offers the advantage of conferring on the polymer mixture the advantageous mechanical properties of the polyamide.

In principle, it is preferred that the number of copolymers per unit area of the interface is large, resulting in a maximum threshold stress. However, too much concentration of copolymers at the interface may affect other properties such as viscosity. Also, it is advantageous to seek a number of copolymers preferably between 3 and 50%, this percentage corresponding to a mass yield of reaction relative to the species in default. Beyond 50%, polymeric mixtures having properties different from those desired are obtained.

[Applications]

Because of the properties mentioned above, the polymeric mixtures described are particularly useful for the manufacture of metal-polymer composites, such as sandwich structures or polymer-coated metal facings. This type of composite is particularly sought after in the automotive industry.

Composites are most often made of a polymeric mixing film according to the invention applied to a sheet or between two metal sheets.

The metal is most often a steel, the choice of the specific type will depend on the intended application. Thus, in the automotive field, the types of steel usually used are the ES grade (EN DC01 to DC06) and the HLE grade (EN H240 LA to H400 LA). The thickness of the metal sheets used for this application will generally be between 0.1 mm to 3 mm. The metal may be untreated but most often it will be provided with one or more coatings in order to improve its properties, such as for example a coating of zinc or zinc alloy made by galvanizing or electrodeposition, or a surface treatment, a primer, a paint or varnish base or a layer of oil.

The metal-polymer composites may be manufactured by any of the methods known per se.

Thus, according to another aspect, the invention provides a method of manufacturing a metal-polymer composite comprising the steps of:

at. providing a first sheet of metal, optionally heated to the melting temperature of the polymer;

b. applying a polymeric mixture according to the invention to the first sheet of metal to form a metal-polymer composite;

vs. where appropriate, applying a second sheet of metal, optionally heated to the melting temperature of the polymer, to the polymeric mixture to form a metal-polymer-metal composite; and

d. heating the composite until the polymer mixture melts in contact with the metal to complete the adhesion.

Preferably, the polymeric mixture is pre-extruded to form a polymeric film. However, it is also possible to extrude the polymeric film directly onto the first sheet of metal or to co-laminate the polymeric film between the two metal sheets in a single step.

The extrusion is preferably carried out in a co-rotating twin screw extruder. The thickness of the polymeric film depends on the application and is preferably between 0.05 and 5 mm, and more preferably between 0.2 and 1 mm.

The polymeric mixture described provides an adherent polymeric surface with products such as sealants, structural adhesives and crash adhesives. It is thus possible to polymer overmold the polymeric surface of the metal-polymer composites obtained.

Also, according to another aspect, the invention is directed to multilayer structures comprising, between two metal sheets, a film of the polymeric mixture as described above, in particular metal-polymer-metal composites, such as sandwich structures, as well as facings. comprising a metal sheet coated with the polymer mixture according to the invention. These products are light, rigid, stampable, inexpensive and resistant to cataphoresis and therefore particularly useful in the automotive industry. Depending on the applications, it may be used sandwich structures having two facings of different types and / or thickness. The invention will be described in more detail by means of the examples given below and the appended figures, which show:

FIG. 1: a diagram of the reaction between the functional groups of the polymers at the interface of a polymeric mixture according to the invention;

Fig.2: a schematic representation of the interaction between modified polyolefin nodules forming a three-dimensional network;

FIG. 3: Scanning electron microscopy (SEM) photographs of the mixtures of Examples 1 to 7 after extraction of the polyolefin phase;

Fig.4: a graph of the strain rate dE / dt as a function of the stress σ of the mixtures of Examples 1 to 4;

Fig.5: a graph of the strain rate dE / dt as a function of the stress σ of the mixtures of Examples 5 to 7;

Fig.6: a graph of the elastic modulus G 'for different frequencies of the mixtures of Examples 1 - 4;

Fig.7: a graph of the elastic modulus G 'for different frequencies of the mixture of Examples 5 to 7;

Fig.8: a diagram of the experimental setup for the evaluation of the resistance to cataphoresis of a sandwich (DP 500 steel, thickness = 0.5 mm and polymeric mixture thickness = 1 mm); and

FIG. 9: the adhesion evaluated by the pad test for the mixtures of Examples 1 -

EXAMPLES EXAMPLE 1 (PA11 / POE-MAH)

After preliminary drying in a vacuum oven at 70 ° C, are introduced 60 g of polyamide 11 Arkema (PA11 Rilsan ^®) and 40 g of polyethylene-octene copolymer modified with maleic anhydride 1.5% (POE-MAH, Tabond 8010 available from Silon International) in a Haake Rheomix 600 internal mixer heated to a temperature of 210 ° C (20 ° C above the melting temperature of the polyamide).

The mixture is kneaded between 5 and 10 minutes until the torsional torque exerted on the blades of the mixer is stabilized.

The polymeric mixture obtained is then pressed in a Lescuyer 200bars hydraulic press to make films 1 mm thick.

It is concluded from the scanning electron microscope observation after extraction of the toluene-modified polyolefin at 110 ° C. for 2 to 7 days that the Two-phase mixture comprises a continuous phase and modified polyolefin nodules whose diameter is of the order of 300 nm (see FIG. 3).

EXAMPLE 2-4 (PA11 / POE-MAH)

In order to evaluate the impact of the proportion of polyamide and polyolefin in the mixture, the protocol indicated in the preceding example is repeated but by varying the proportions of the polymers according to Table 1 below.

It is concluded from the scanning electron microscope observation after extraction of the modified polyolefin carried out as described in the previous example (see FIG. 3) that the mixture is biphasic for all the examples and that it is present for the examples 1 and 2 modified polyolefin nodules with a diameter of the order of 300 nm and for Examples 3 and 4 an aspect at the boundary of the co-continuity.

EXAMPLE 5 (PA1 1 / PE-MA Na ⁺ )

After drying in a vacuum oven at 80 ° C., 60 g of Arkema polyamide 11 (PA 1 Rilsan ^® ) and 40 g of low density polyethylene modified with 0.5% by weight of partially acid anhydride are introduced. neutralized (against sodium-ion) (ionomer Priex 35392 ^® available from Addcomp Holland BV) in a Haake Rheomix 600 internal mixer heated to a temperature of 210 ° C (20 ° C higher than the polyamide melting temperature).

It is concluded from the scanning electron microscope observation after extraction of the toluene-modified polyolefin carried out as described in Example 1 that the mixture is biphasic comprising a continuous phase and nodules of modified polyolefin, the diameter of which is order of 170 nm. EXAMPLE 6 (PA1 1 / POE-AH / Si)

In order to study the effect of a mineral filler on the threshold stress, a polymeric mixture is prepared which additionally contains a silica as a filler.

More specifically, a polymer mixture is prepared according to the protocol indicated in Example 1, using as polyamide 49.5 g of a polyamide 1 1 (PA 1 1 Rilsan ^® available from Arkema), and as modified polyolefin 40 5 g of polyethylene octene modified with maleic anhydride at a level of 1.5% (POE-MAH, Tabond 8010 available from Silon International) as well as 10 g of hydrophilic fumed silica with a specific surface area of about 200 m ² / g (Wacker fumed silica HDK N 20). This mixture has a polyamide: polyolefin equivalent to the mixture of Example 2 (55% PA11 and 45% POE-MAH).

It is concluded from the scanning electron microscope observation after extraction of the modified polyolefin carried out as described in Example 1 that the mixture is biphasic comprising a continuous phase and modified polyolefin nodules whose diameter is of the order of 300. nm (see Figure 3). EXAMPLE 7 (PA1 1 / PE-MANa ⁺ )

After preliminary drying in a vacuum oven at 80 ° C, are introduced 60 g of polyamide 11 Arkema (PA11 Rilsan ^®) and 40 g high density polyethylene modified with 0.05% by weight of anhydride maleic acid partially neutralized (against sodium-ion) (ionomer Priex 33101 ^® available from Addcomp Holland BV) in a Haake Rheomix 600 internal mixer heated to a temperature of 210 ° C (20 ° C higher than the polyamide melting temperature).

It is concluded from the scanning electron microscope observation after extraction of the toluene-modified polyolefin carried out as described in Example 1 that the mixture is biphasic comprising a continuous phase and nodules of modified polyolefin, the diameter of which is order of 200 to 250 nm.

Table 1: Composition of Polymeric Mixtures

EVALUATION OF POLLUTION MIXTURES

A. Threshold constraint

The rheological measurements were performed on an imposed stress rheometer equipped with a cone-plane geometry (Rheometrics Scientific SR5 model).

The polymer mixture sample was formed into a pellet 1 mm thick and 25 mm in diameter. This sample was subjected to an instantaneous stress varying between 0 and 5000 Pa. The evolution of the deformation is followed by a displacement sensor. The measurement temperature is a function of the matrix polymer and is identical to the mixing temperature (20 ° C above the melting peak of the polyamide).

The threshold stress is determined from the graph in which the strain rate is plotted against the stress. When the curve forms a threshold, the melt mixture exhibits a threshold stress fluid behavior. The threshold stress is determined graphically on the curve as the limit stress beyond which the rate of deformation increases.

It can be seen that all the mixtures of Examples 1 to 7 have a threshold stress at the temperature under consideration. The results are illustrated in detail in the FIGS. 4 and 5. The threshold stress values determined from the curves are given in Table 2 below.

Table 2: Threshold stress of polymer mixtures

The gradual increase of the threshold stress observed for Examples 1 to 4 from 50 Pa to 700 Pa can be explained by an increase in the density of nodules, since their diameters are unchanged, and the subsequent reinforcement of the interactions between nodules and chain entanglement phenomena, which in turn induce a slower chain relaxation and the appearance of a rubbery plateau.

It is also noted that the presence of ionic groups seems to have a favorable effect in terms of the threshold stress.

Finally, the addition of mineral fillers has a significant effect on the threshold stress of the mixtures of the invention, since it makes it possible to go from 200 Pa for Example 2 to 2000 Pa for Example 6.

B. Elastic module

The complex shear modulus was determined on an RMS 800 imposed deformation rheometer with plane-plane geometry over a frequency range of 0.01-100 rad / s, the sample having previously been formed into a 1 mm pellet. thick and 25 mm in diameter. The measurement temperature being identical to the mixing temperature (20 ° C. above the melting peak of the polyamide).

This technique makes it possible to study the vioscoelasticity in the linear domain of the polymer in the molten state. Qualitatively, the existence of a threshold stress is correlated with the observation of a plateau at low frequencies on the curve representing the elastic modulus G 'as a function of its stress frequency. In this area, the material is has a rubber-like appearance where the crosslinking points are replaced by strong interactions of the physical entanglement type.

The results are illustrated in Figures 6 and 7.

Figure 6 illustrates the shape of the curve obtained. The mixture of Example 1 has an elastic modulus at low low frequencies and whose tray is not visible because located outside the range examined. The increase of the proportion of modified polyolefin in the formulation from 40% to 55% by weight causes a gradual increase in the elastic modulus and the appearance of a plateau at around 10 000 Pa at low frequency.

FIG. 7 shows the curve obtained for the mixtures according to Examples 5, 6 and 7. It can be seen that the elastic modulus has a plateau at low frequencies for all of these mixtures. Moreover, there is a significant impact of the addition of charges at the elastic modulus. Indeed, the addition of charges makes it possible to reduce the value of the elastic modulus of the mixture of Example 6 (mass ratio polyamide / polyolefin 55:45, as Example 2) to that of Example 4 (see Figure 6), whose polyolefin share is however greater.

C. Creep

The creep behavior of the polymeric mixtures according to the invention was evaluated experimentally as follows.

Sandwich structures with a dimension of 90x50x2mm were manufactured with a DP 500 grade steel 0.5 mm thick galvanized, degreased (gardoclean ^® 5183) and chemically treated on the surface (Granodine ^® 1455 sold by Henkel diluted 2% in the water). The steel / polymer / steel sandwiches were developed in press using shims to keep the thickness of the polymer constant around 0.8 mm.

The conditions during cataphoresis are then simulated by holding the sandwich vertically using a magnet that retains one of the two facings. This sandwich is then placed for 1 hour in an oven whose temperature is 235 ° C to ensure complete melting of the polymer. The assembly of the test is schematically illustrated in FIG.

The resistance of the sandwich to the test is evaluated by visual inspection of the sandwich structures after the test. When no sliding of the facings is observed for the sandwich structures, it is considered that the polymeric mixture exhibits the creep resistance necessary for resistance to cataphoresis.

All the sandwiches evaluated are resistant to the creep test. D. Adherence

The adhesion of the polymer blends to the steel was evaluated by two separate tests. Tear pull test

In this test, the adhesion of the polymer to the metal is evaluated by means of a tensile pull test according to ISO 4624.

The principle is to measure the maximum force required to pull a cylindrical steel stud treated with Granodine ^® 1455 (sold by the company Henkel) bonded to the 0.5 mm thick DP500 steel substrate of ArcelorMittal also treated with Granodine ^® 1455 via a film of the polymer mixture with a thickness of 100μ ^ηη . The test is performed on an Instron machine coupled to a computer that records the force exerted as a function of displacement.

It is observed that the breaks are mixed, that is to say that the rupture takes place both at the steel / polymer interface (adhesive rupture) but also in the polymeric film (cohesive failure).

The results are illustrated in FIG. 9. It can be seen that the force required to tear off the stud is very satisfactory for the mixtures according to examples 1 to 4. Peel test

In this test, the adhesion of the polymer to the metal is evaluated by means of a peel test according to standard NF T 76-112.

In order to carry out this test, Lescuyer 200 bar steel / polymer / steel sandwiches are prepared by controlling the thickness of the polymer around 0.7 mm by means of shims. The sandwiches obtained are then cut into strips of 20 cm long and 2.5 cm wide.

Before making the peeling of the primers are done so as to obtain an adhesive break between the polymer and the metal. Then, the peeling is performed by vertical traction over a length of 10 cm by an Instron peeling machine. The rupture is mixed also in this case.

It is found that a very good adhesion is observed for all the compositions examined.

In conclusion, the reaction at the interfaces of the functional groups of the polyamide and of the modified polyolefin in the mixtures according to the invention results in a structure 010 052675

19

specific generating rheological properties characterized by the appearance of a threshold stress.

Such polymeric blends have the qualities required for use in the manufacture of metal-polymer composites as they are extrudable, rigid, exhibit proper stamping behavior and excellent adhesion to the metal.

The presence of a threshold stress also makes it possible to ensure resistance to cataphoresis even in the molten state since the mixture does not flow until the stress does not exceed the threshold stress. The value of the threshold stress can be optimized in particular in terms of the choice of polyamide and the proportion of the modified polyolefin in the mixture, but also by addition of fillers.

Claims

1. A two-phase polymeric mixture comprising:

(a) a polyamide having a melting point of at most 210 ° C,

(b) a modified polyolefin having carboxylic functions,

whose rheological behavior in the molten state is characterized by the existence of a threshold stress. 2. Mixture according to claim 1, comprising 30 to 70% by weight of polyamide.

3. - A mixture according to claims 1 or 2, comprising 30 to 70% by weight of modified polyolefin.

4. - Blend according to one of claims 1 to 3, wherein the modified polyolefin is a modified polyethylene.

5. - Blend according to one of claims 1 to 4, wherein the modified polyolefin is modified with maleic anhydride.

6. - Blend according to one of claims 1 to 5, wherein the modified polyolefin is modified with 0.01 to 20% by weight of compound having carboxylic functions relative to the final weight of the modified polyolefin.

7. - Mixture according to one of claims 1 to 6, wherein the polyamide is a polyamide 11.

8. - Blend according to one of claims 1 to 7, comprising a continuous phase consisting essentially of polyamide and a dispersed or co-continuous phase composed essentially of polyolefin.

9. The mixture of claim 8, wherein the dispersed phase is in the form of nodules whose average diameter is preferably less than 500 nm.

10. - Blend according to one of claims 1 to 9, further comprising 5 to 20% by weight of fillers.

11. - Mixture according to one of claims 1 to 10, having a threshold stress of at least 50 Pa.

12. - Process for preparing the polymer mixture according to one of the preceding claims, comprising the steps of:

(b) mixing the polyamide and the modified polyolefin at a temperature above the melting peak of the polyamide. 3. A method of manufacturing a metal-polymer composite comprising the steps of:

(ii) applying a polymeric mixture according to one of claims 1 to 10 to the first metal sheet to form a metal-polymer composite;

(ii) where appropriate, applying a second metal sheet optionally heated to the polymer melt temperature, to the polymeric mixture to form a metal-polymer-metal composite; and

14. Sandwich structures comprising, between two metal sheets, a film of the polymer mixture according to one of claims 1 to 11.

15. - Siding comprising a metal sheet coated with the polymer mixture according to one of claims 1 to 11.